Use of cationically modified, particle-shaped, hydrophobic polymers as addition agents in textile rinsing or care products and as addition agents in detergents

ABSTRACT

The invention relates to the use of cationically-modified, particle-shaped, hydrophobic polymers as addition agents in rinsing, care, detergent, and cleaning products. The surface of said polymers is cationically modified by means of a coating of cationic polymers and the particle size of said polymers ranges from 10 nm to 100 μm.

The invention relates to the use of cationically modified, particulate,hydrophobic polymers as additive to rinse or care compositions and asadditive to detergents, and also to rinse compositions, carecompositions and detergents which comprise the cationically modified,particulate, hydrophobic polymers.

Dispersions of particles of hydrophobic polymers, in particular aqueousdispersions of synthetic polymers and of waxes are used in the art formodifying the properties of surfaces. For example, aqueous dispersionsof finely divided hydrophobic polymers are used as binders in papercoating slips for the coating of paper, or as coating compositions. Thedispersions applied in each case to a substrate in accordance withcustomary methods, e.g. by knifecoating, painting, saturation orimpregnation, are dried. During this, the dispersely distributedparticles form a continuous film on the respective surface.

Aqueous washing, rinsing, cleaning and care processes are, by constrast,usually carried out in a heavily diluted liquor, where the ingredientsof the formulation used in each case do not remain on the substrate, butinstead are disposed of with the wastewater. Modification of surfaceswith dispersed hydrophobic particles is possible in the abovementionedprocesses only to an entirely unsatisfactory degree. Thus, for example,U.S. Pat. No. 3,580,853 discloses a detergent formulation whichcomprises a water-insoluble finely divided substance, such as biocidesand certain cationic polymers which increase the deposition andretention of the biocides on the surface of the ware.

Furthermore, U.S. Pat. No. 5,476,660 discloses the principle of usingpolymeric retention agents for cationic or zwitterionic dispersions ofpolystyrene or wax which contain an active substance embedded within thedispersed particles. These dispersed particles are referred to as“carrier particles”, because they adhere to the treated surface, wherethey release the active substance e.g. upon use in surfactant-containingformulations.

U.S. Pat. No. 3,993,830 discloses the application of a nonpermanent soilrepellant finish on a textile ware by treating the textile ware with adiluted aqueous solution which comprises a polycarboxylate polymer and awater-soluble salt of a polyvalent metal. Suitable polycarboxylatepolymers are, preferably, water-soluble copolymers of ethylenicallyunsaturated monocarboxylic acids and alkyl acrylates. The mixtures areused, in the case of domestic textile washing, in the rinse cycle of thewashing machine.

It is an object of the present invention to provide a further method forthe modification of textile surfaces.

We have found that this object is achieved according to the invention bythe use of cationically modified, particulate, hydrophobic polymers, thesurface of which has been cationically modified by coating with cationicpolymers, and the particle size of which is 10 nm to 100 μm, as additiveto rinse or care compositions for textiles and as additive todetergents.

The cationically modified, particulate, hydrophobic polymers areobtainable, for example, by treatment of aqueous dispersions ofparticulate, hydrophobic polymers having a particle size of from 10 nmto 100 μm with an aqueous solution or dispersion of a cationic polymer.This is carried out most simply by combining an aqueous dispersion ofparticulate, hydrophobic polymers having a particle size of from 10 nmto 100 μm with an aqueous solution or dispersion of a cationic polymer.The cationic polymers are preferably used in the form of aqueoussolutions, but it is also possible to use aqueous dispersions ofcationic polymers, the dispersed particles of which have an averagediameter up to 1 μm. In most cases, the two components are mixed at roomtemperature, although the mixing can also be carried out at temperaturesof e.g. 0° to 100° C., provided that the dispersions do not coagulateupon heating.

The dispersions of the particulate, hydrophobic polymers can bestabilized using an anionic emulsifier or protective colloid. Otherdispersions which can be used with equal success are free fromprotective colloids and emulsifiers and comprise, however, for thispurpose as hydrophobic polymers, copolymers which contain at least oneanionic monomer in copolymerized form. Such dispersions of copolymershaving anionic groups may optionally additionally comprise an emulsifierand/or a protective colloid. Preference is given here to using anionicemulsifiers and/or protective colloids.

In the treatment of the anionically adjusted dispersions of thehydrophic polymers with an aqueous solution of a cationic polymer, thecharge of the originally anionically dispersed particles is reversed sothat, following the treatment, they preferably carry a cationic charge.Thus, for example, cationically modified dispersions of particulate,hydrophobic polymers have, in 0.1% strength by weight aqueousdispersion, an interface potential of −5 to +50 mV, preferably from −2to +25 mV, in particular from 0 to +15 mV. The interface potential isdetermined by measuring the electrophoretic mobility in dilute aqueousdispersion and the pH of the designated application liquor.

The pH of the aqueous dispersions of the cationically modified,particulate, hydrophobic polymers is, for example, 1 to 12 and ispreferably in the range from 2 to 10, in particular in the range from2.5 to 8. If particles of the polymers having a content of more than 10%by weight of anionic monomers are used, the pH of the aqueousdispersions is 1 to 7.5, preferably 2 to 5.5, in particular 2.5 to 5.

The hydrophobic polymers used according to the invention are insolublein water at the application pH. They are present therein in the form ofparticles having an average particle size of 10 nm to 100 μm, preferably25 nm to 20 μm, particularly preferably 40 nm to 2 μm and in particular60 to 800 nm, and can be obtained from the aqueous dispersions aspowders. The average particle size of the hydrophobic polymers can bedetermined, for example, under the electron microscope or using lightscattering experiments.

In a preferred embodiment, the particles of the hydrophobic polymers tobe used according to the invention exhibit pH-dependent solubility andswelling behavior. At a pH below 6.5, particularly below 5.5 and inparticular below 5, the particles are water-insoluble and retain theirparticular character upon dispersion in concentrated and also in diluteaqueous media. By contrast, hydrophobic polymer particles containingcarboxyl groups swell in water under neutral and alkaline conditions.This behavior of hydrophobic polymers having anionic groups is knownfrom the literature, cf. M. Siddiq et al., who, in Colloid. Polym. Sci.277, 1172-1178 (1999), report on the behavior of particles ofmethacrylic acid/ethyl acrylate copolymers in an aqueous medium.

Hydrophobic polymers are obtainable, for example, by polymerization ofmonomers from the group of alkyl esters of C₃-C₅-monoethylenicallyunsaturated carboxylic acids and monohydric C₁-C₂₂-alcohols,hydroxyalkyl esters of C₃-C₅-monoethylenically unsaturated carboxylicacids and dihydric C₂-C₄-alcohols, vinyl esters of saturatedC₁-C₁₈-carboxylic acids, ethylene, propylene, isobutylene,C₄-C₂₄-α-olefins, butadiene, styrene, α-methylstyrene, acrylonitrile,methacrylonitrile, tetrafluoroethylene, vinylidene fluoride,fluoroethylene, chlorotrifluoroethylene, hexafluoropropene, esters oramides of C₃-C₅-monoethylenically unsaturated carboxylic acids withamines or alcohols containing perfluoroalkyl groups, alkyl and vinylesters of carboxylic acids containing perfluoroalkyl groups or mixturesthereof. These may be homopolymers or copolymers.

Examples of hydrophobic copolymers are copolymers of ethyl acrylate andvinyl acetate, copolymers of butyl acrylate and styrene, copolymers of(meth)acrylic esters of the perfluoroalkyl-substituted alcohols of theformula CF₃—(C₂F₄)_(n)—(CH₂)_(m)—OH or C₂F₅—(C₂F₄)_(n)—(CH₂)_(m)—OH(n=1-10, m=0-10) with (meth)acrylic esters and/or (meth)acrylic acid,copolymers of ethylene and tetrafluoroethylene, and copolymers of butylacrylate and vinyl acetate. Said copolymers can contain the monomers incopolymerized form in any ratios.

The anionic character of the polymers mentioned can be achieved, forexample, by copolymerizing the monomers which form the basis of thecopolymers in the presence of small amounts of anionic monomers such asacrylic acid, methacrylic acid, styrenesulfonic acid,acrylamido-2-methyl-propanesulfonic acid, vinyl sulfonate and/or maleicacid and optionally in the presence of emulsifiers and/or protectivecolloids.

The anionic character of the mentioned polymers can, however, also beachieved by carrying out the copolymerization in the presence of anionicprotective colloids and/or anionic emulsifiers.

The anionic character of the mentioned polymers can, however, also beachieved by emulsifying or dispersing the finished polymers in thepresence of anionic protective colloids and/or anionic emulsifiers.

Hydrophobic polymers comprise, for example,

-   -   (a) 40 to 100% by weight, preferably 50 to 90% by weight,        particularly preferably 60 to 75% by weight, of at least one        water-insoluble nonionic monomer,    -   (b) 0 to 60% by weight, preferably 1 to 55% by weight,        particularly preferably 5 to 50% by weight, in particular 15 to        40% by weight, of at least one monomer containing carboxyl        groups or salts thereof,    -   (c) 0 to 25% by weight, preferably 0 to 15% by weight, of a        monomer containing sulfonic acid and/or phosphonic acid groups,        or salts thereof,    -   (d) 0 to 55% by weight, preferably 0 to 40% by weight, of at        least one water-soluble nonionic monomer and    -   (e) 0 to 10% by weight, preferably 0 to 5% by weight, of at        least one polyethylenically unsaturated monomer        in copolymerized form.

Polymers which contain at least one anionic monomer b) or c) can be usedwithout additional anionic emulsifiers or protective colloids. Polymerswhich contain less than 0.5% of anionic monomers are in most cases usedtogether with at least one anionic emulsifer and/or protective colloid.

Preferred monomers (a) are methyl acrylate, ethyl acrylate, n-butylacrylate, sec-butyl acrylate, tert-butyl acrylate, ethylhexyl acrylate,hydroxyethyl acrylate, hydroxypropyl acrylate, methyl methacrylate,n-butyl methacrylate, (meth)acrylic esters of theperfluoroalkyl-substituted alcohols CF₃—(C₂F₄)_(n)—(CH₂)_(m)—OH orC₂F₅—(C₂F₄)_(n)—(CH₂)_(m)—OH (n=2-8, m is 1 or 2), vinyl acetate, vinylpropionate, styrene, ethylene, propylene, butylene, isobutene,diisobutene and tetrafluoroethylene, and particularly preferred monomers(a) are methyl acrylate, ethyl acrylate, n-butyl acrylate, tert-butylacrylate and vinyl acetate.

Preferred hydrophobic polymers contain less than 75% by weight of anonionic water-insoluble monomer (a) in copolymerized form, thehomopolymers of which have a glass transition temperature T_(g) of morethan 60° C.

Preferred monomers (b) are acrylic acid, methacrylic acid, maleic acidor maleic half-esters of C₁-C₈-alcohols.

Monomers of group (c) are, for example,acrylamido-2-methylpropanesulfonic acid, vinylsulfonic acid,methallylsulfonic acid, vinylsulfonic acid, and the alkali metal andammonium salts of these monomers.

Suitable monomers (d) are, for example, acrylamide, methacrylamide,N-vinylformamide, N-vinylacetamide, N-vinylpyrrolidone,N-vinyloxazolidone, methylpolyglycol acrylate, methylpolyglycolmethacrylate and methylpolyglycol acrylamide. Preferred monomers (d) arevinylpyrrolidone, acrylamide and N-vinylformamide.

Suitable polyethylenically unsaturated monomers (e) are, for example,acrylic esters, methacrylic esters, allyl ethers or vinyl ethers of atleast dihydric alcohols. The OH groups of the parent alcohols can becompletely or partially etherified or esterified; however, thecrosslinkers contain at least two ethylenically unsaturated groups.Examples are butanediol diacrylate, hexanediol diacrylate,trimethylolpropane triacrylate and tripropylene glycol diacrylate.

Further suitable polyethylenically unsaturated monomers (e) are e.g.allyl esters of unsaturated carboxylic acids, divinylbenzene,methylenebisacrylamide and divinylurea.

Such copolymers can be prepared by the known methods of solution,precipitation, suspension or emulsion polymerization of the monomersusing free-radical polymerization initiators. Preferably, theparticulate hydrophobic polymers are obtained by the process of emulsionpolymerization in water. The polymers have, for example, molar masses offrom 1000 to 2 million, preferably from 5000 to 500 000, and in mostcases the molar masses of the polymers are in the range from 10 000 to150 000.

To limit the molar masses of the polymers it is possible to addcustomary regulators during the polymerization. Examples of typicalregulators are mercapto compounds, such as mercaptoethanol orthioglycolic acid.

Apart from said polymerization processes, other processes for thepreparation of the polymer particles to be used according to theinvention are also suitable. Thus, it is possible, for example, toprecipitate out polymers by lowering the solubility of the polymers inthe solvent. Such a method consists, for example, in dissolving acopolymer containing acid groups in a suitable water-miscible solvent,and metering in water in an excess such that the pH of the initialcharge is lower by at least 1 than the equivalent pH of the copolymer.Equivalent pH is understood as meaning the pH at which 50% of the acidicgroups of the copolymer have been neutralized. In this process, it maybe necessary to add dispersion auxiliaries, pH regulators and/or saltsin order to obtain stable finely divided dispersions.

For the modification of finely divided hydrophobic polymers to be usedaccording to the invention which contain anionic groups, it is possibleto additionally add, during the dispersion, other polymers whichpartially or completely react or associate therewith and precipitateout. Such polymers are, for example, polysaccharides, polyvinyl alcoholsand polyacrylamides.

Particulate, hydrophobic polymers can also be prepared by emulsifying amelt of the hydrophobic polymers in a controlled manner. For this, thepolymer or a mixture of the polymers with further additives is, forexample, melted and, under the action of strong shear forces, e.g. in anUltra-Turrax, water is metered in in an excess such that the pH of theinitial charge is lower by at least one than the equivalent pH of thepolymer. Here, it may in some instances be necessary to add emulsifyingauxiliaries, pH regulators and/or salts in order to obtain stable finelydivided dispersions. Also in the case of this variant of the preparationof finely divided polymer dispersions, it is possible to co-useadditional polymers such as polysaccharides, polyvinyl alcohols orpolyacrylamides, particularly when the hydrophobic polymer containsanionic groups.

A further method for the preparation of finely divided hydrophobicpolymers which contain anionic groups consists in treating aqueous,alkaline solutions of the polymers, preferably under the action ofstrong shear forces, with an acid.

Examples of anionic emulsifiers are anionic surfactants and soaps.Anionic surfactants which may be used are alkyl and alkenyl sulfates,sulfonates, phosphates and phosphonates, alkyl- andalkenylbenzenesulfonates, alkyl ether sulfates and phosphates, saturatedand unsaturated C₁₀-C₂₅-carboxylic acids and salts thereof.

Additionally, it is possible to use nonionic and/or betainicemulsifiers. A description of suitable emulsifiers is given, forexample, in Houben Weyl, Methoden der organischen Chemie [Methods oforganic Chemistry], Volume XIV/1, Makromolekulare Stoffe [MacromolecularSubstances], Georg Thieme Verlag, Stuttgart, 1961, pages 192 to 208.

Examples of anionic protective colloids are water-soluble anionicpolymers. Here, it is possible to use very different types of polymer.Anionically substituted polysaccharides and/or water-soluble anioniccopolymers of acrylic acid, methacrylic acid, maleic acid, maleichalf-esters, vinylsulfonic acid, styrenesulfonic acid oracrylamidopropanesulfonic acid are preferably used with other vinylicmonomers. Suitable anionically substituted polysaccharides are, forexample, carboxymethylcellulose, carboxymethyl starch, oxidized starch,oxidized cellulose and other oxidized polysaccharides, and thecorresponding derivatives of the partially degraded polysaccharide.

Suitable water-soluble anionic copolymers are, for example, copolymersof acrylic acid with vinyl acetate, acrylic acid with ethylene, acrylicacid with acrylamide, acrylamidopropanesulfonic acid with acrylamide oracrylic acid with styrene.

Other nonionic and/or betainic protective colloids can additionally beused. An overview of customarily used protective colloids is given inHouben Weyl, Methoden der organischen Chemie, Volume XIV/1,Makromolekulare Stoffe, Georg Thieme Verlag, Stuttgart, 1961, pages 411to 420.

For the preparation of particulate, hydrophobic polymers use ispreferably made of anionic polymeric protective colloids which lead toprimary particles having anionic groups on the particle surface.

The cationically modified, particulate, hydrophobic polymers to be usedaccording to the invention are obtainable by coating the surface of theanionically dispersed, particulate, hydrophobic polymers with cationicpolymers. Cationic polymers which can be used are all cationic syntheticpolymers which are soluble or finely dispersible in aqueous solvents andwhich contain amino and/or ammonium groups. Examples of such cationicpolymers are polymers containing vinylamine units, polymers containingvinylimidazole units, polymers containing quaternary vinylimidazoleunits, condensates of imidazole and epichlorohydrin, crosslinkedpolyamidoamines, crosslinked polyamidoamines grafted with ethylenimine,polyethylenimines, alkoxylated polyethylenimines, crosslinkedpolyethylenimines, amidated polyethylenimines, alkylatedpolyethylenimines, polyamines, amine/epichlorohydrin polycondensates,alkoxylated polyamines, polyallylamines, polydimethyldiallylammoniumchlorides, polymers containing basic (meth)acrylamide or (meth)acrylicester units, polymers containing basic quaternary (meth)acrylamide or(meth)acrylic ester units, and/or lysine condensates.

For the preparation of polymers containing vinylamine units, thestarting materials are, for example, open-chain N-vinylcarboxamides ofthe formula:

in which R¹ and R² may be identical or different and are hydrogen andC₁-C₆-alkyl. Suitable monomers are, for example, N-vinylformamide(R¹═R²═H in formula I), N-vinyl-N-methylformamide, N-vinylacetamide,N-vinyl-N-methylacetamide, N-vinyl-N-ethyl-acetamide,N-vinyl-N-methylpropionamide and N-vinylpropionamide. For thepreparation of the polymers, said monomers can be polymerized alone, inmixtures with one another or together with other monoethylenicallyunsaturated monomers. Preference is given to starting from homopolymersor copolymers of N-vinylformamide. Polymers containing vinylamine unitsare known, for example, from U.S. Pat. No. 4,421,602, EP-A-0 216 387 andEP-A-0 251 182. They are obtained by hydrolysis of polymers whichcontain the monomers of the formula I in copolymerized form, with acids,bases or enzymes.

Suitable monoethylenically unsaturated monomers which are copolymerizedwith the N-vinylcarboxamides are all compounds copolymerizabletherewith. Examples thereof are vinyl esters of saturated carboxylicacids having 1 to 6 carbon atoms, such as vinyl formate, vinyl acetate,vinyl propionate and vinyl butyrate, and vinyl ethers, such asC₁-C₆-alkyl vinyl ethers, e.g. methyl or ethyl vinyl ethers. Furthersuitable comonomers are ethylenically unsaturated C₃-C₆-carboxylicacids, for example acrylic acid, methacrylic acid, maleic acid, crotonicacid, itaconic acid and vinyl acetic acid, and the alkali metal andalkaline earth metal salts thereof, esters, amides and nitrites of saidcarboxylic acids, for example methyl acrylate, methyl methacrylate,ethyl acrylate and ethyl methacrylate.

Cationic polymers are also understood as meaning amphoteric polymerswhich have a net cationic charge, i.e. the polymers contain both anionicand cationic monomers in copolymerized form, although the molarproportion of the cationic units present in the polymer is greater thanthat of the anionic units.

Further suitable carboxylic esters are derived from glycols orpolyalkylene glycol, where in each case only one OH group is esterified,e.g. hydroxyethyl acrylate, hydroxyethyl methacrylate, hydroxypropylacrylate, hydroxybutyl acrylate, hydroxypropyl methacrylate,hydroxybutyl methacrylate, and acrylic monoesters of polyalkyleneglycols having a molar mass of from 500 to 10 000. Further suitablecomonomers are esters of ethylenically unsaturated carboxylic acids withamino alcohols, such as, for example, dimethylaminoethyl acrylate,dimethylaminoethyl methacrylate, diethylaminoethyl acrylate,diethylaminoethyl methacrylate, dimethylaminopropyl acrylate,dimethylaminopropyl methacrylate, diethylaminopropyl acrylate,dimethylaminobutyl acrylate and diethylaminobutyl acrylate. The basicacrylates can be used in the form of the free bases, the salts withmineral acids, such as hydrochloric acid, sulfuric acid or nitric acid,the salts with organic acids, such as formic acid, acetic acid,propionic acid or of the sulfonic acids or in quaternized form. Suitablequaternizing agents are, for example, dimethyl sulfate, diethyl sulfate,methyl chloride, ethyl chloride or benzyl chloride.

Further suitable comonomers are amides of ethylenically unsaturatedcarboxylic acids, such as acrylamide, methacrylamide, and N-alkylmono-and diamides of monoethylenically unsaturated carboxylic acids havingalkyl radicals of 1 to 6 carbon atoms, e.g. N-methylacrylamide,N,N-dimethylacrylamide, N-methylmethacrylamide, N-ethylacrylamide,N-propylacrylamide and tert-butylacrylamide, and basic(meth)acrylamides, such as dimethylaminoethylacrylamide,dimethylaminoethylmethacrylamide, diethylaminoethylacrylamide,diethylaminoethylmethacrylamide, dimethylaminopropylacrylamide,diethylaminopropylacrylamide, dimethylaminopropylmethacrylamide anddiethylaminopropylmethacrylamide.

Also suitable as comonomers are N-vinylpyrrolidone, N-vinyl-caprolactam,acrylonitrile, methacrylonitrile, N-vinylimidazole and substitutedN-vinylimidazoles, such as e.g. N-vinyl-2-methyl-imidazole,N-vinyl-4-methylimidazole, N-vinyl-5-methylimidazole,N-vinyl-2-ethylimidazole and N-vinylimidazolines, such asN-vinylimidazoline, N-vinyl-2-methylimidazoline andN-vinyl-2-ethylimidazoline. Apart from being used in the form of thefree bases, N-vinylimidazoles and N-vinylimidazolines can also be usedin a form neutralized with mineral acids or organic acids or inquaternized form, the quaternization preferably being effected usingdimethyl sulfate, diethyl sulfate, methyl chloride or benzyl chloride.Also suitable are diallyldialkylammonium halides, such asdiallyldimethylammonium chloride.

Further suitable comonomers are monomers containing sulfo groups, suchas, for example, vinylsulfonic acid, allylsulfonic acid,methallylsulfonic acid, styrenesulfonic acid, the alkali metal orammonium salts of these acids or 3-sulfopropyl acrylate, the content inthe amphoteric copolymers of cationic units exceeding the content ofanionic units, such that overall the polymers have a cationic charge.

The copolymers comprise, for example,

-   -   99.99 to 1 mol %, preferably 99.9 to 5 mol % of        N-vinylcarboxamides of the formula I and    -   0.01 to 99 mol %, preferably 0.1 to 95 mol % of other        monoethylenically unsaturated monomers copolymerizable therewith        in copolymerized form.

To prepare polymers containing vinylamine units, preference is given tostarting from homopolymers of N-vinylformamide or of copolymersobtainable by copolymerization of

-   -   N-vinylformamide with    -   vinyl formate, vinyl acetate, vinyl propionate, acrylonitrile,        N-vinylcaprolactam, N-vinylurea, acrylic acid,        N-vinylpyrrolidone or C₁-C₆-alkyl vinyl ethers        and subsequent hydrolysis of the homopolymers or of the        copolymers with the formation of vinylamine units from the        copolymerized N-vinylformamide units, the degree of hydrolysis        being, for example, 0.1 to 100 mol %.

The hydrolysis of the above-described polymers is carried out inaccordance with known processes by the action of acids, bases orenzymes. In this process, the copolymerized monomers of the aboveformula I produce, as a result of cleaving off the group:

where R² has the meaning given therefor in formula I, polymers whichcontain vinylamine units of the formula:

in which R¹ has the meaning given in formula I. If acids are used ashydrolysis agents, the units III are in the form of the ammonium salt.

The homopolymers of the N-vinylcarboxamides of the formula I and theircopolymers can be hydrolyzed to 0.1 to 100 mol %, preferably 70 to 100mol %. In most cases, the degree of hydrolysis of the homopolymers andcopolymers is 5 to 95 mol %. The degree of hydrolysis of thehomopolymers is synonymous with the content of vinylamine units in thepolymers. In the case of copolymers which contain vinyl esters incopolymerized form, in addition to the hydrolysis of theN-vinylformamide units, hydrolysis of the ester groups can arise withthe formation of vinyl alcohol units. This is the case particularly whenthe hydrolysis of the copolymers is carried out in the presence ofsodium hydroxide solution. Copolymerized acrylonitrile is likewisechemically changed during the hydrolysis. Here, amide groups or carboxylgroups, for example, form. The homopolymers and copolymers containingvinylamine units may optionally contain up to 20 mol % of amidine units,which are formed, for example, by the reaction of formic acid with twoadjacent amino groups or by intramolecular reaction of one amino groupwith an adjacent amide group e.g. of copolymerized N-vinylformamide. Themolar masses of the polymers containing vinylamine units are, forexample, 1000 to 10 million, preferably 10 000 to 5 million (determinedby light scattering). This molar mass range corresponds, for example, toK values of from 5 to 300, preferably 10 to 250 (determined inaccordance with H. Fikentscher in 5% strength aqueous sodium chloridesolution at 25° C. and a polymer concentration of 0.5% by weight).

The polymers containing vinylamine units are preferably used insalt-free form. Salt-free aqueous solutions of polymers containingvinylamine units can be prepared, for example, from the above-describedsalt-containing polymer solutions using ultrafiltration over suitablemembranes at cut-offs of, for example, 1000 to 500 000 daltons,preferably 10 000 to 300 000 daltons. The aqueous solutions of otherpolymers containing amino and/or ammonium groups described below canalso be obtained in salt-free form by means of ultrafiltration.

Polyethylenimines are prepared, for example, by polymerization ofethylenimine in aqueous solution in the presence of acid-eliminatingcompounds, acids or Lewis acids. Polyethylenimines have, for example,molar masses up to 2 million, preferably from 200 to 500 000. Particularpreference is given to using polyethylenimines having molar masses offrom 500 to 100 000. Also suitable are water-soluble, crosslinkedpolyethylenimines which are obtainable by reacting polyethylenimineswith crosslinkers, such as epichlorohydrin or bischlorohydrin ethers ofpolyalkylene glycols having 2 to 100 ethylene oxide and/or propyleneoxide units. Amidic polyethylenimines which are obtainable, for example,by amidation of polyethylenimines with C₁-C₂₂-monocarboxylic acids arealso suitable. Further suitable cationic polymers are alkylatedpolyethylenimines and alkoxylated polyethylenimines. During thealkoxylation, 1 to 5 ethylene oxide or propylene oxide units are used,for example, per NH unit in polyethylenimine.

Further suitable amino- and/or ammonium-containing polymers arepolyamidoamines, which are obtainable, for example, by condensingdicarboxylic acids with polyamines. Suitable polyamidoamines areobtained, for example, by reacting dicarboxylic acids having 4 to 10carbon atoms with polyalkylenepolyamines which contain 3 to 10 basicnitrogen atoms in the molecule. Suitable dicarboxylic acids are, forexample, succinic acid, maleic acid, adipic acid, glutaric acid, subericacid, sebacic acid and terephthalic acid. In the preparation of thepolyamidoamines it is also possible to use mixtures of dicarboxylicacids as well as mixtures of two or more polyalkylenepolyamines.Examples of suitable polyalkylenepolyamines are diethylenetriamine,triethylenetetramine, tetraethylenepentamine, dipropylenetriamine,tripropylenetetramine, dihexamethylenetriamine,aminopropylethylenediamine and bisaminopropylethylenediamine. For thepreparation of the polyamido amines, the dicarboxylic acids andpolyalkylenepolyamines are heated to relatively high temperatures, e.g.to temperatures in the range from 120 to 220, preferably 130 to 180° C.The water which forms during the condensation is removed from thesystem. Lactones or lactams of carboxylic acids having 4 to 8 carbonatoms may also be used in the condensation. 0.8 to 1.4 mol of apolyalkylenepolyamine, for example, are used per mole of dicarboxylicacid.

Further amino-containing polymers are polyamidoamines grafted withethylenimine. They are obtainable from the above-describedpolyamidoamines by reaction with ethylenimine in the presence of acidsor Lewis acids, such as sulfuric acid or boron trifluoride etherates, attemperatures of, for example, 80 to 100° C. Compounds of this type aredescribed, for example, in DE-B-24 34 816.

The optionally crosslinked polyamidoamines, which have optionally beenadditionally grafted with ethylenimine prior to crosslinking, are alsosuitable as cationic polymers. The crosslinked polyamidoamines graftedwith ethylenimine are water-soluble and have, for example, an averagemolecular weight of from 3000 to 1 million daltons. Customarycrosslinkers are, for example, epichlorohydrin or bischlorohydrin ethersof alkylene glycols and polyalkylene glycols.

Further examples of cationic polymers which contain amino and/orammonium groups are polydiallyldimethylammonium chlorides. Polymers ofthis type are likewise known.

Further suitable cationic polymers are copolymers of, for example, 1 to99 mol %, preferably 30 to 70 mol % of acrylamide and/or methacrylamideand 99 to 1 mol %, preferably 70 to 30 mol % of cationic monomers, suchas dialkylaminoalkylacrylamide, dialkylaminoalkylacrylic esters and/ordialkylaminoalkylmethacrylamide and/or dialkylaminoalkylmethacrylicesters. The basic acrylamides and methacrylamides are likewisepreferably in a form neutralized with acids or in quaternized form.Examples which may be mentioned are N-trimethylammoniumethylacrylamidechloride, N-trimethylammoniumethylmethacrylamide chloride,N-trimethylammoniumethyl methacrylate chloride, N-trimethylammoniumethylacrylate chloride, trimethylammoniumethylacrylamide methosulfate,trimethylammoniumethylmethacrylamide methosulfate,N-ethyldimethylammoniumethylacrylamide ethosulfate,N-ethyldimethylammoniumethylmethacrylamide ethosulfate,trimethylammoniumpropylacrylamide chloride,trimethylammoniumpropylmethacrylamide chloride,trimethylammoniumpropylacrylamide methosulfate,trimethylammoniumpropylmethacrylamide methosulfate andN-ethyldimethylammoniumpropylacrylamide ethosulfate. Preference is givento trimethylammoniumpropylmethacrylamide chloride.

Further suitable cationic monomers for the preparation of(meth)acrylamide polymers are diallyldimethylammonium halides and basic(meth)acrylates. Suitable examples are copolymers of 1 to 99 mol %,preferably 30 to 70 mol %, of acrylamide and/or methacrylamide and 99 to1 mol %, preferably 70 to 30 mol %, of dialkylaminoalkyl acrylatesand/or methacrylates, such as copolymers of acrylamide andN,N-dimethylaminoethyl acrylate or copolymers of acrylamide anddimethylaminopropyl acrylate. Basic acrylates or methacrylates arepreferably in a form neutralized with acids or in quaternized form. Thequaternization can be carried out, for example, with methyl chloride orwith dimethyl sulfate.

Further suitable cationic polymers which have amino and/or ammoniumgroups are polyallylamines. Polymers of this type are obtained byhomopolymerization of allylamine, preferably in a form neutralized withacids or in quaternized form, or by a copolymerization of allylaminewith other monoethylenically unsaturated monomers which are describedabove as comonomers for N-vinylcarboxamides.

The cationic polymers have, for example, K values of from 8 to 300,preferably 100 to 180 (determined in accordance with H. Fikentscher in5% strength aqueous sodium chloride solution at 25° C. and a polymerconcentration of 0.5% by weight). At a pH of 4.5, they have, forexample, a charge density of at least 1, preferably at least 4 meq/g ofpolyelectrolyte.

Examples of preferred cationic polymers are polydimethyldiallylammoniumchloride, polyethylenimine, polymers containing vinylamine units,copolymers of acrylamide or methacrylamide, containing basic monomers incopolymerized form, polymers containing lysine units, or mixturesthereof. Examples of cationic polymers are:

Copolymers of 50 mol % vinylpyrrolidone and 50 mol %trimethylammoniumethyl methacrylate methosulfate, M_(w) 1000 to 500 000,

Copolymers of 30 mol % acrylamide and 70 mol % trimethylammoniumethylmethacrylate methosulfate, M_(w) 1000 to 1 000 000,

Copolymers of 70 mol % acrylamide and 30 mol % dimethylaminoethylmethacrylamide, M_(w) 1000 to 1 000 000,

Copolymers of 50 mol % hydroxyethyl methacrylate and 50 mol %2-dimethylaminoethyl methacrylamide, M_(w) 1000 to 500 000.

It is also possible to incorporate minor amounts (<10% by weight) ofanionic comonomers as polymerized units, e.g. acrylic acid, methacrylicacid, vinylsulfonic acid or alkali metal salts of said acids.

Copolymer of 70 mol % hydroxyethyl methacrylate and 30 mol %2-dimethylaminoethylmethacrylamide; copolymer of 30 mol % vinylimidazolemethochloride, 50 mol % dimethylaminoethyl acrylate, 15 mol %acrylamide, 5 mol % acrylic acid,

polylysines having an M_(w) of from 250 to 250 000, preferably 500 to100 000, and lysine cocondensates having molar masses M_(w) of from 250to 250 000, the cocondensible component being, for example, amines,polyamines, ketene dimers, lactams, alcohols, alkoxylated amines,alkoxylated alcohols and/or nonprotogenic amino acids,

vinylamine homopolymers, 1 to 99 mol % of hydrolyzedpolyvinylformamides, copolymers of vinylformamide and vinyl acetate,vinyl alcohol, vinylpyrrolidone or acrylamide having molar masses offrom 3 000 to 500 000,

vinylimidazole homopolymers, vinylimidazole copolymers withvinylpyrrolidone, vinylformamide, acrylamide or vinyl acetate havingmolar masses of from 5 000 to 500 000, and quaternary derivativesthereof,

polyethylenimines, crosslinked polyethylenimines or amidatedpolyethylenimines having molar masses of from 500 to 3 000 000,

amine/epichlorohydrin polycondensates which contain, as amine component,imidazole, piperazine, C₁-C₈-alkylamines, C₁-C₈-dialkylamines and/ordimethylaminopropylamine and which have a molar mass of from 500 to 250000,

polymers containing basic (meth)acrylamide or (meth)acrylic ester units,polymers containing basic quaternary (meth)acrylamide or (meth)acrylicester units and having molar masses of from 10 000 to 2 000 000.

In order to cationically modify anionically dispersed, particulate,hydrophobic polymers, the latter can, in addition to a treatment withcationic polymers, also be treated with polyvalent metal ions and/orcationic surfactants. Coating of the particles with polyvalent metalions is achieved by, for example, adding an aqueous solution of at leastone water-soluble, polyvalent metal salt to an aqueous dispersion ofanionically dispersed hydrophobic polymers, or dissolving awater-soluble, polyvalent metal salt therein, the modification of theanionically dispersed hydrophobic particles which cationic polymersbeing carried out either before, at the same time as or after thistreatment. Suitable metal salts are, for example, the water-solublesalts of Ca, Mg, Ba, Al, Zn, Fe, Cr or mixtures thereof. Otherwater-soluble heavy metal salts which are derived, for example, from Cu,Ni, Co and Mn can also in principle be used, but are not desired in allapplications. Examples of water-soluble metal salts are calciumchloride, calcium acetate, magnesium chloride, aluminum sulfate,aluminum chloride, barium chloride, zinc chloride, zinc sulfate, zincacetate, iron(II) sulfate, iron(III) chloride, chromium(III) sulfate,copper sulfate, nickel sulfate, cobalt sulfate and manganese sulfate.Preference is given to using the water-soluble salts of Ca, Mg, Al andZn for the cationization.

The charge of the anionically dispersed hydrophobic polymers can also bechanged using cationic polymers and cationic surfactants. Of potentialsuitability for this purpose are cationic surfactants of very differentstructures. An overview of a selection of suitable cationic surfactantsis given in Ullmanns Encyclopaedia of Industrial Chemistry, SixthEdition, 1999, Electronic Release, Chapter “Surfactants”, Chapter 8,Cationic Surfactants.

Particularly suitable cationic surfactants are, for example,

-   C₇-C₂₅-alkylamines,-   C₇-C₂₅-N,N-dimethyl-N-(hydroxyalkyl)ammonium salts, mono- and    di-(C₇-C₂₅)alkyldimethylammonium compounds quaternized with    alkylating agents,-   ester quats, such as, for example, quaternary esterified mono-, di-    or trialkanolamines which have been esterified with    C₈-C₂₂-carboxylic acids,-   imidazoline quats, such as 1-alkylimidazolinium salts of the    formulae IV or V:    where-   R¹=C₁-C₂₅-alkyl or C₂-C₂₅-alkenyl,-   R²=C₁-C₄-alkyl or hydroxyalkyl and-   R³=C₁-C₄-alkyl, hydroxyalkyl or a radical R¹—CO—X—(CH₂)_(n)— where    X=O or NH and n=2 or 3, and    where at least one radical R¹=C₇-C₂₂-alkyl or C₇-C₂₂-alkenyl.

For many commercial applications and everyday domestic applications, themodification of the properties of textiles with dispersions is ofsignificance. It is not always possible to carry out the modification ofsurfaces by impregnation, spraying and painting processes withconcentrated dispersions. It is frequently desirable to carry out themodification using a rinsing of the textile material to be treated witha heavily diluted liquor containing an active substance or by sprayingon a heavily diluted aqueous formulation. Here, it is often desirable tocombine the modification of the surface of textiles in association witha washing, cleaning and/or care or impregnation of the surface.Particularly suitable textiles are cotton fabric and cotton blendfabric. In addition it is also possible to treat carpets and furniturecoverings in accordance with the invention.

The modification of the surfaces of textile materials can consist, forexample, in a hydrophobicization, soil release finishing,soil-repellancy finishing, a reinforcement of the fiber composite andprotection against chemical or mechanical influences or damage.

The cationically modified, particulate, hydrophobic polymers are usedfor the modification of surfaces of the materials mentioned above by wayof example, as additive to rinse or care compositions for textiles, andas detergents. They can, for example, be used as the sole activecomponent in aqueous rinse and care compositions and, depending on thecomposition of the polymer, for example, facilitate soil release duringa subsequent wash, bring about lower soil adhesion during use of thetextiles, improve the structural retention of fibers, improve theretention of shape and structure of fabrics, effect hydrophobicizationof the surface of the ware, and improve the handle. The concentration ofthe cationically modified, particulate, hydrophobic polymers in the caseof use in a rinse or care bath, in the detergent liquor or the cleaningbath is, for example, 0.0002 to 1.0% by weight, preferably 0.0005 to0.25% by weight, particularly preferably 0.002 to 0.05% by weight.

The treatment of laundry or textile surfaces is carried out usingaqueous liquors which contain, for example, 2.5 to 300 ppm, preferably 5to 200 ppm and in particular 10 to 100 ppm of at least one cationicpolymer and optionally in addition up to 10 mmol/l, preferably up to 5mmol/l, particularly preferably up to 3.5 mol/l, of water-soluble saltsof polyvalent metals, in particular salts of Ca, Mg or Zn and/or up to 2mmol/l, preferably up to 0.75 mmol/l, of water-soluble Al salts and/orup to 600 ppm, preferably up to 300 ppm, of cationic surfactants.

Compositions for the treatment of laundry and textile surfaces can beliquid, in gel form or solid.

The compositions may, for example, have the following composition:

-   -   (a) 0.05 to 40% by weight of cationically modified, particulate,        hydrophobic polymers, the surface of which has been cationically        modified by coating with cationic polymers, and the particle        size of which is 10 nm to 100 μm,    -   (b) 0.01 to 10% by weight of at least one cationic polymer, and    -   (c) 0 to 80% by weight of at least one customary additive, such        as acids or bases, inorganic builders, organic cobuilders,        further surfactants, polymeric color transfer inhibitors,        polymeric antiredeposition agents, soil release polymers,        enzymes, complexing agents, corrosion inhibitors, waxes,        silicone oils, light protection agents, dyes, perfume, solvents,        hydrotropic agents, salts, thickeners and/or alkanolamines.

Laundry aftertreatment and laundry care compositions in liquid or gelform comprise, for example

-   -   (a) 0.1 to 30% by weight of particulate, hydrophobic polymers        which contain at least one group of anionic ethylenically        unsaturated monomers in copolymerized form, have a particle size        of from 10 nm to 100 μm and have been dispersed in water    -   (b) 0.05 to 20% by weight of an acid, such as formic acid,        citric acid, adipic acid, succinic acid, oxalic acid or mixtures        thereof,    -   (c) 0.1 to 10% by weight of at least one cationic polymer,    -   (d) 0 to 30% by weight of at least one water-soluble salt of Mg,        Ca, Zn or Al and/or of a cationic surfactant,    -   (e) 0 to 10% by weight of at least one other customary        ingredient, such as perfume, other surfactants, silicone oil,        light protection agent, dyes, complexing agent, antiredeposition        agent, soil release polyester, color transfer inhibitor,        nonaqueous solvent, hydrotropic agent, thickener and/or        alkanolamine and    -   (f) water to make up to 100% by weight.

The above-described laundry aftertreatment and laundry care compositionscan be formulated on the basis of the same ingredient or as solidcompositions. Examples of possible solid forms are powders, granules andtablets.

To prepare solid compositions, it may be necessary to additionally addextenders, spraying agents, agglomeration auxiliaries, coatingauxiliaries or binders. To ensure the action and good dissolutionbehavior, it may additionally be necessary to add components which aiddissolution, such as readily water-soluble salts, polymericdisintegrants or combinations of acids and hydrogencarbonate.

In a preferred embodiment, laundry aftertreatment and laundry carecompositions comprise, as component (a), 0.5 to 25% by weight ofparticulate, hydrophobic polymers which contain, in copolymerized form,25 to 60% by weight of an ethylenically unsaturated monomer whichcontains at least one carboxylic acid group, have a particle size offrom 10 nm to 100 μm and have been dispersed using an anionic emulsifierand/or an anionic protective colloid in water.

The compositions of this preferred embodiment are particularly suitablefor achieving soil-release-promoting properties. Soilings which arise inthe service phase are more readily removed from laundry aftertreated inthis way in the subsequent washing operation.

In a further preferred embodiment, laundry aftertreatment and laundrycare compositions comprise, as component (a), 0.5 to 25% by weight ofparticulate, hydrophobic polymers which contain, in copolymerized form,0.1 to 10% by weight of an ethylenically unsaturated monomer whichcontains at least one carboxylic acid group, and at least 80% by weightof a water-insoluble ethylenically unsaturated nonionic monomer, have aparticle size of from 10 nm to 100 μm and have been dispersed using ananionic emulsifier and/or an anionic protective colloid in water.

The compositions of this preferred embodiment are particularly suitablefor achieving hydrophobicizing or impregnating properties. Water isabsorbed or let through by laundry aftertreated in this way to asignificantly lesser extent.

Laundry aftertreatment and laundry care compositions comprise in afurther prerferred embodiment, as component (a) 0.5 to 25% by weight ofparticulate, hydrophobic polymers which contain, in copolymerized form,10 to 100% by weight of an ethylenically unsaturated monomer whichcontains fluorine substituents, have a particle size of from 10 nm to100 μm and have been dispersed using an anionic emulsifier and/or ananionic protective colloid in water.

The compositions of this preferred embodiment are particularly suitablefor achieving soil repellency properties, in particular oil and greasesoil repellency properties. Oil and grease soiling is absorbed by fabricaftertreated in this way to a lesser extent.

Suitable acids are mineral acids, such as sulfuric acid or phosphoricacid, and organic acids, such as carboxylic acids or sulfonic acids.Strong acids, such as sulfuric acid, phosphoric acid, or sulfonic acidsare usually used here in partially neutralized form.

The cationic modification of the particulate, hydrophobic polymers ispreferably carried out prior to use in the aqueous treatmentcompositions, although it can also be carried out during the preparationof the aqueous treatment compositions or the use of anionicallyemulsified, particulate, hydrophobic polymers having a particle size offrom 10 nm to 100 μm by, for example, mixing aqueous dispersions of thesuitable particulate, hydrophobic polymers with the other constituentsof the treatment composition in each case in the presence of cationicpolymers and optionally water-soluble salts of polyvalent metals and/orcationic surfactants.

In a particular embodiment it is also possible to add the anionicparticles or formulations containing these particles directly to therinse, wash or cleaning liquor if it is ensured that sufficient amountsof cationic polymers and optionally polyvalent metal ions and/orcationic surfactants are present in the liquor in dissolved form. Forexample, it is possible to use the anionic hydrophobic particles orformulations containing these particles in liquors having a content ofcationic polymers of from 2.5 to 300 ppm and optionally of water-solublesalts of Ca, Mg or Zn of more than 0.5 mmol/l, preferably more than 1mmol/l, particularly preferably more than 2 mmol/l. If cationicsurfactants are used, they are used, for example, in concentrations offrom 50 to 100 ppm, preferably 75 to 500 ppm and in particular from 100to 300 ppm, in the aqueous liquor.

The anionic particles or formulations containing these particles canalso be metered in before, after or at the same time as a formulationcontaining cationic polymers and optionally cationic surfactants.

Examples of the composition of typical nonionic dispersions which can beprocessed to rinse and care compositions and detergents by mixing withcationic polymers and optionally water-soluble salts of polyvalentmetals and/or cationic surfactants and also other components are thedispersions I to V described below, the dispersed particles of which canin each case be observed, upon investigation using an electronmicroscope, as discrete particles having the given average particlediameter:

Dispersion I

40% strength by weight aqueous dispersion of a polymer of 56% by weightof ethyl acrylate, 33% by weight of methacrylic acid and 11% by weightof acrylic acid having an average particle diameter of 288 nm. Thedispersion comprised 1.25% by weight of an anionic surfactant asemulsifier and 20% by weight of a low molecular weight starch asprotective colloid. It had a pH of 4.

Dispersion II

30% strength by weight aqueous dispersion of a polymer of 66% by weightof ethyl acrylate, 4% by weight of methacrylic acid, 26% by weight ofacrylic acid and 4% by weight of acrylamide. The average diameter of thedispersed particles of the dispersion was 176 nm. The dispersioncomprised 0.8% by weight of an anionic surfactant as emulsifier and hada pH of 4.

Dispersion III

30% strength by weight aqueous dispersion of a polymer of 50% by weightof ethyl acrylate and 50% by weight of methacrylic acid with an averagediameter of the dispersed particles of 123 nm. The dispersion comprised0.8% by weight of an anionic surfactant as emulsifier and had a pH of 4.

Dispersion IV

35% strength by weight dispersion of a polymer of 64% by weight ofn-butyl acrylate, 33% by weight of methyl methacrylate and 4% by weightof acrylic acid. The average diameter of the dispersed particles of thedispersion was 80 nm. The dispersion comprised 1.5% by weight of ananionic surfactant as emulsifier and had a pH of 6.

Dispersion V

Anionic fluoropolymer dispersion Nuva® FTA-4 (Clariant)

Using dispersions I to III it is possible to prepare typicalformulations with soil release action according to the invention whichare used, for example, during domestic washing in the rinse cycle of thewashing machine in a dose of from 0.5 to 5 g/l, preferably 1 to 3 g/l:

Formulation I

-   50% by weight of one of the above-described dispersions I to III-   1.5% by weight of formic acid-   0.5% by weight of polyethyleneimine of molar mass M_(w) 25 000-   water to make up to 100% by weight.    Formulation II-   50% by weight of one of the above-described dispersions I to III-   4.5% by weight of formic acid-   5% by weight of calcium chloride-   1.0% by weight of polyethyleneimine of molar mass M_(w) 5 000-   water to make up to 100% by weight.    Formulation III-   50% by weight of one of the above-described dispersions I to III-   2% by weight of 2N sulfuric acid-   1.0% by weight of crosslinked high molecular weight    polyethyleneimine-   2.0% by weight of polyvinylpyrrolidone of molar mass M_(w) 50 000-   water to make up to 100% by weight.    Formulation IV-   50% by weight of one of the above-described dispersions I to III-   2% by weight of 2N sulfuric acid-   0.5% by weight of polyethyleneimine of molar mass M_(w) 25 000-   5% by weight of an ester quat (methyl quat of the di-tallow fatty    acid ester of triethanolamine)-   water to make up to 100% by weight.

The formulations can optionally comprise further constituents such ascustomary soil release polymers for polyesters, antiredeposition agents,perfume, dyes, enzymes, hydrotropic agents, solvents, nonionicsurfactants, silicone oil, a textile softener and/or a thickener.

Using dispersions IV and V it is possible to prepare typicalformulations with impregnating effects according to the invention whichare used, for example, during domestic washing in the rinse cycle of thewashing machine in a dose of from 0.5 to 5 g/l, preferably 1 to 3 g/l.

Formulation V for Water Repellency Impregnation

-   50% by weight of the above-described dispersion IV-   1% by weight of polyethyleneimine of molar mass M_(w) 25 000-   5% by weight of polyvinylpyrrolidone of molar mass M_(w) 50 000-   water to make up to 100% by weight    Formulation VI for Oil Repellency Impregnation-   50% by weight of the above-described dispersion V-   0.2% by weight of polyethyleneimine of molar mass M_(w) 25 000-   5% by weight of calcium acetate-   water to make up to 100% by weight

The formulations can optionally comprise further constituents such ascustomary soil release polymers for polyesters, antiredeposition agents,perfume, dyes, enzymes, hydrotropic agents, solvents, nonionicsurfactants, silicone oil, a textile softener and/or a thickener.

The following aqueous dispersions of copolymers, the dispersed particlesof which have an average diameter of from 10 nm to 100 μm and which havein each case been dispersed using an anionic dispersant, for example,are suitable as hydrophobicizing, soil-repelling or fiber reinforcingadditive to rinse or care compositions, and detergents:

-   copolymers of butyl acrylate and styrene,-   copolymers of butyl acrylate and vinyl acetate and-   tetrafluoroethylene polymers.

The anionic character of the abovementioned dispersions may optionallybe additionally established by polymerizing the polymers in the presenceof small amounts (up to 10% by weight) of anionic monomers, such asacrylic acid, styrenesulfonic acid, vinylphosphonic acid oracrylamido-2-methylpropanesulfonic acid. These dispersions arepreferably cationically modified by treatment with water-solublecationic polymers, or the cationic modification of the dispersions iscarried out during the preparation of the rinse or care compositions.The resulting cationically modified, particulate, hydrophobic polymersto be used according to the invention have, upon use in the rinse cycleof domestic washing machines, a hydrophobicizing, fiber reinforcing andsoil repellancy action on the textiles treated therewith.

The invention further provides a solid detergent formulation whichcomprises:

-   -   (a) 0.05 to 20% by weight of cationically modified, particulate,        hydrophobic polymers, the surface of which has been cationically        modified by coating with cationic polymers and optionally        additionally with polyvalent metal ions and/or cationic        surfactants, and the particle size of which is 10 nm 20 to 100        μm,    -   (b) 0.1 to 40% by weight of at least one nonionic, cationic        and/or anionic surfactant,    -   (c) 0 to 50% by weight of an inorganic builder,    -   (d) 0 to 20% by weight of an organic cobuilder, and    -   (e) 0 to 60% by weight of other customary ingredients, such as        extenders, enzymes, perfume, other surfactants, complexing        agents, corrosion inhibitors, bleaches, bleach activators,        bleach catalysts, color transfer inhibitors, antiredeposition        agents, soil release polyesters, dyes, dissolution improvers        and/or disintegrants,        and a detergent formulation in liquid or gel form which        comprises    -   (a) 0.05 to 20% by weight of cationically modified, particulate,        hydrophobic polymers, the surface of which has been cationically        modified by coating with at least one cationic polymer and        optionally additionally with polyvalent metal ions and/or        cationic surfactants, and the particle size of which is 10 nm to        100 μm,    -   (b) 0.1 to 40% by weight of at least one nonionic, cationic        and/or anionic surfactant,    -   (c) 0 to 20% by weight of an inorganic builder,    -   (d) 0 to 10% by weight of an organic cobuilder,    -   (e) 0 to 20% by weight of other customary ingredients, such as        soda, enzymes, perfume, other surfactants, complexing agents,        corrosion inhibitors, bleaches, bleach activators, bleach        catalysts, color transfer inhibitors, antiredeposition agents,        soil release polyesters, dyes, nonaqueous solvents, hydrotropic        agents, thickeners and/or alkanolamines and    -   (f) 0 to 90% by weight of water.

The surfactants, builders, cobuilders, complexing agents, solvents,color transfer inhibitors, soil release polyesters, bleaches, bleachactivators, antiredeposition agents, enzymes, perfumes, solvents,thickeners, oils, waxes, hydrotropic agents, foam suppressors,silicones, brighteners and dyes specified in the various formulationscan be combined within the scope of the feed substances usuallycustomary in dishwashing, care, laundry washing and cleaningformulations. For typical ingredients, reference may be made to thechapter Detergents (Part 3, Detergent Ingredients, Part 4, HouseholdDetergents and Part 5, Institutional Detergents) in Ullmann'sEncyclopedia of Industrial Chemistry, Sixth Edition, 2000 ElectronicVersion 2.0.

Preferred nonionic surfactants are, for example, alkoxylatedC₈-C₂₂-alcohols, such as fatty alcohol ethoxylates and oxo alcoholalkoxylates which have been alkoxylated with 3 to 15 mol of ethyleneoxide and optionally additionally with 1 to 4 mol of propylene oxideand/or butylene oxide, and also block polymers of ethylene oxide andpropylene oxide with a molar mass of from 900 to 12 000 and a weightratio of ethylene oxide to propylene oxide of from 1 to 20.

Particularly preferred nonionic surfactants are C₁₃/C₁₅ oxo alcoholethoxylates and C₁₂/C₁₄ fatty alcohol ethoxylates which have beenalkoxylated with 3 to 11 mol of ethylene oxide per mole of alcohol orfirstly with 3 to 10 mol of ethylene oxide and then with 1 to 3 mol ofpropylene oxide per mole of alcohol.

Preferred anionic surfactants are, for example, alkylbenzenesulfonateswith linear or branched C₆-C₂₅-alkyl groups, fatty alcohol and oxoalcohol sulfates with C₈-C₂₂-alkyl groups and fatty alcohol or oxoalcohol ether sulfates from C₈-C₂₂-alcohols which have been ethoxylatedwith 1 to 5 mol of ethylene oxide per mole of alcohol and have beensulfated on the OH end-group of the ethoxylate.

Formulations according to the invention are preferably formulated tohave a low content of anionic surfactants, and are particularlypreferably free from anionic surfactants. If anionic surfactants areused in the formulations, preference is given to using ether sulfates.

Preferred solvents are alcohols, such as methanol, ethanol, isopropanol,n-butanol, isobutanol, ethylene glycol, propylene glycol, diethyleneglycol, triethylene glycol, dipropylene glycol, tripropylene glycol andbutanediol.

Preferably, only small amounts of, and particularly preferably no,solvents are added to the formulations.

Preferred builders are alkali metal carbonates, phosphates,polyphosphates, zeolites and silicates. Particularly preferred buildersare zeolite A, zeolite P, phyllosilicates, soda and trisodiumpolyphosphate.

Preferred complexing agents are nitrilotriacetic acid,methylglycinediacetic acid and ethylenediamine tetraacetate.

Preferred cobuilders are acrylic acid homopolymers, acrylic acid/maleicacid copolymers, polyaspartic acid and citric acid. Particularlypreferred cobuilders are acrylic acid homopolymers of molar mass 1 500to 30 000 and acrylic acid/maleic acid copolymers with a molar ratio ofthe monomers of from 10:1 to 1:2 and molar masses of from 4 000 to 100000.

Preferred soil release polyesters are polyesters of terephthalic acid,ethylene glycol and polyethylene glycol, where polyethylene glycols withmolar masses of from 1 000 to 5 000 are incorporated by condensation,and also those polyesters in which terephthalic acid has been replacedin an amount up to 50 mol % by sulfocarboxylic acids orsulfodicarboxylic acids.

Preferred color transfer inhibitors are polyvinylpyrrolidone of molarmasses 8 000 to 70 000, vinylimidazole/vinylpyrrolidone copolymers witha molar ratio of the monomers of from 1:10 to 2:1 and molar masses offrom 8 000 to 70 000, and poly-4-vinylpyridine N-oxides of molar massesfrom 8 000 to 70 000.

Preferred enzymes are proteases, lipases, cellulases and amylases.

Formulations according to the invention can optionally additionallycomprise further protective colloids for stabilizing the disperse state.This is of particular importance particularly in the case of liquidformulations in order to prevent coagulation. The protective colloidscan, however, also be added advantageously to solid formulations inorder to prevent coagulation during use.

Protective colloids which may be used are water-soluble polymers, inparticular water-soluble nonionic polymers. Suitable protective colloidspreferably have molar masses of from 8 000 to 200 000, particularlypreferably from 5 000 to 75 000, in particular from 10 000 to 50 000.

Suitable protective colloids are, for example, polyvinylpyrrolidone,polyethylene glycol, block polymers of ethylene oxide and propyleneoxide, enzymatically degraded starches and polyacrylamides.

Use of the cationically modified dispersions to be used according to theinvention achieves, particularly on cotton and cellulose fibers, asignificantly higher soil release action than with known water-solublesoil release polymers.

The percentages in the examples are percentages by weight.

EXAMPLES

For the examples and comparative examples, the dispersion I was used.

Dispersion I

40% strength by weight aqueous dispersion of a polymer of 56% by weightof ethyl acrylate, 33% by weight of methacrylic acid and 11% by weightof acrylic acid having an average particle diameter of 288 nm. Thedispersion comprised 1.25% by weight of an anionic surfactant asemulsifier and 20% by weight of a low molecular weight starch asprotective colloid. It had a pH of 4.

Comparative Example 1

The anionic dispersion I was brought to a content of 0.040% usingdeionized water of pH 4. A white cotton fabric was suspended in themagnetically stirred liquor for 30 min. The absorbance of the liquor wasmeasured at 520 nm using a vis-spectrometer. Over the course of 30 min,no change in the absorbance was observed. Electron micrographs showedvirtually no coating of the cotton fibers with dispersion particles.

Example 1

The dispersion I was brought to a content of particles of 10% by weightusing deionized water of pH 4. This dispersion was metered in, withstirring using a magnetic stirrer, to an equal volume of a 1% strengthsolution, adjusted to pH 4, of a high molecular weight crosslinkedpolyethylenimine (molar mass 2 000 000) over the course of 30 min. Thisgave a dispersion which was stable for hours.

This dispersion was diluted to a content of 0.040% using deionized waterof pH 4. A white cotton fabric was suspended in the magnetically stirredliquor for a period of 30 min. The absorbance of the liquor was measuredat 520 nm using a vis-spectrometer over 30 minutes. A considerabledecrease in absorbance was observed.

Example 2

Example 1 was repeated except that the cationic polymer used for coatingthe dispersion particles was a copolymer of vinylimidazole andvinylpyrrolidone (monomer ratio 1:1) of molar mass 10 000.

Example 3

Example 1 was repeated except that the cationic polymer used for coatingthe dispersion particles was a polycondensate of imidazole andepichlorohydrin (molar ratio of the components 1:1) of molar mass 12000.

TABLE 1 Absorbance of the dispersions measured at 520 nm in a 1 cm cell.The values give the absorbance of the diluted dispersion prior toemersion of the cotton fabric and after 30 minutes. MeasurementComparative Example Example Example time point Example 1 1 2 3 t = 0 min1.0 0.99 0.99 1.00 t = 30 min 1.0 0.65 0.77 0.69

A comparison of Examples 1 to 3 with the Comparative Example 1 showsthat, where the particles are coated with the cationic polymers,considerably higher proportions of the hydrophobic particles areadsorbed on the surface of the cotton fabric than in the absorbance ofthe cationic polymers. This finding is confirmed by electronmicrographs.

Examples 4 to 6 and Comparative Examples 2 to 4

To test the soil release properties of afterrinse formulationscontaining particles according to the invention, the following washingexperiments were carried out:

Cotton fabric was prewashed with dispersion I. In comparative experiment3, the dispersion was used in the absence of a cationic polymer. InExamples 4 to 6, the dispersion particles were firstly coated with 10%by weight of the cationic polymers as described in Examples 1 to 3. Theprewashed fabrics were soiled with lipstick composition and then washedwith a standard detergent (Ariel Futur). To evaluate the soil releaseaction, the reflectance of the soiled fabric was measured before andafter washing and from this, in a known manner together with thereflectance value of the white cotton fabric, the soil release wasdetermined in % soil release.

Washing Conditions

Prewash

-   Washing device: Launder-O-meter-   Prewash temperature: 20° C.-   Prewash time: 15 min    Main Wash:-   Wash temperature: 40° C.-   Wash time: 30 min-   Water hardness: 3 mmol/l-   Ca/Mg ratio: 3:1

TABLE 2 Washing results: Comparative Comparative Comparative ExampleExample Example Example Example 3 Example 4 4 5 6 Concentration of  0400 mg/l  0 400 mg/l 400 mg/l 400 mg/l particles from dispersion I inthe prewash Cationic polymer none none PEI PEI PVI/VP Imidazole/ epiSoil release action in 32 33 30 52 49 50 the subsequent wash in % soilrelease The abbreviations in the table have the following meanings: PET:Polyethylenimine PVI/VP: Copolymer of vinylimidazole andN-vinylpyrrolidone Imidazole/epi: Condensate of imidazole andepichlorohydrin The results of the washing experiments show that neitherthe anionic polymer dispersion alone nor the cationic polymer alone havea soil release action on the soiling. By contrast, the anionic polymerdispersions coated according to the invention with cationic polymersdisplay a significant improvement in the soil release from cotton.

Example 7

The dispersion IV was brought to a content of particles of 0.4% byweight using deionized water of pH 6. This dispersion was metered in,with stirring, to an equal value of a 0.02% strength by weight solution,adjusted to pH 4, of polyethylenimine of molar mass M_(w) 25 000 overthe course of 30 min. This gave a stable dispersion.

Example 8

To test the water repellency properties of cotton fabrics which havebeen achieved using rinse formulations according to the invention,washing experiments were carried out in the Launder-O-meter. Cottonfabric was washed with a standard commercial detergent and, in the rinsecycle, rinsed with the cationically modified dispersion from example 7.In comparative example 5, no dispersion was added to the rinse bath. Incomparative experiment 6, the non-cationically modified dispersion IVwas added. The rinsed fabric was spun, dried and ironed. To test thewater repellency effect, the fabric was laid flat over the opening of abeaker with a diameter of 5 cm. One droplet of water was appliedcentrally. The time until the drop had completely penetrated into thefabric was determined.

Washing Conditions:

Main Wash:

-   Detergent: Ariel Futur-   Detergent dose: 3.5 g/l-   Wash time: 30 min-   Wash temperature: 40° C.-   Water hardness: 3 mmol/l-   Ca/Mg ratio: 3:1    Rinsing:-   Rinse temperature: 20° C.-   Rinse time: 15 min-   pH: 6-   Liquor ratio: 12.5

TABLE 3 Washing results Comparative Comparative Example example 5example 5 8 Concentration of the — — 400 ppm dispersion from example 7in the rinse cycle Concentration of the — 400 ppm — dispersion IV in therinse cycle Penetration time for 3 sec  12 sec 350 sec the water drop

1. A composition for the treatment of laundry and textile surfaces,which comprises: (a) 0.05 to 40% by weight of cationically modified,particulate, hydrophobic polymers, the surface of which has beencationically modified by coating with cationic polymers, and theparticle size of which is 10 nm to 100 μm, (b) 0.01 to 10% by weight ofat least one cationic polymer, and (c) 0 to 80% by weight of at leastone customary additive, such as acids or bases, inorganic builders,organic cobuilders, surfactants, polymeric color transfer inhibitors,polymeric antiredeposition agents, soil release polymers, enzymes,complexing agents, corrosion inhibitors, waxes, silicone oils, lightprotection agents, dyes, perfume, solvents, hydrotropic agents, salts,thickeners and/or alkanolamines.
 2. A laundry aftertreatment and laundrycare composition in liquid or gel form, which comprises: (a) 0.1 to 30%by weight of particulate, hydrophobic polymers which contain at leastone group of anionic ethylenically unsaturated monomers in copolymerizedform, have a particle size of from 10 nm to 100 μm and have beendispersed in water, (b) 0.05 to 20% by weight of an acid, (c) 0.1 to 10%by weight of at least one cationic polymer, (d) 0 to 30% by weight of atleast one water-soluble salt of Mg, Ca, Zn or Al and/or of a cationicsurfactant, (e) 0 to 10% by weight of at least one other customaryingredient, such as perfume, other surfactants, silicone oil, lightprotection agent, dyes, complexing agent, antiredeposition agent, soilrelease polyester, color transfer inhibitor, nonaqueous solvent,hydrotropic agent, thickener and/or alkanolamine and (f) water to makeup to 100% by weight.
 3. A laundry aftertreatment and laundry carecomposition as claimed in claim 2, which comprises, as component (a),0.5 to 25% by weight of particulate, hydrophobic polymers which contain,in copolymerized form, 25 to 60% by weight of an ethylenicallyunsaturated monomer which contains at least one carboxylic acid group,have a particle size of from 10 nm to 100 μm and have been dispersedusing an anionic emulsifier and/or an anionic protective colloid inwater.
 4. A laundry aftertreatment and laundry care composition asclaimed in claim 2, which comprises, as component (a), 0.5 to 25% byweight of particulate, hydrophobic polymers which contain, incopolymerized form, 0.1 to 10% by weight of an ethylenically unsaturatedmonomer which contains at least one carboxylic acid group and at least80% by weight of a water-insoluble ethylenically unsaturated nonionicmonomer, have a particle size of from 10 nm to 100 μm and have beendispersed using an anionic emulsifier and/or an anionic protectivecolloid in water.
 5. A laundry aftertreatment and laundry carecomposition as claimed in claim 2, which comprises, as component (a),0.5 to 25% by weight of particulate, hydrophobic polymers which contain,in copolymerized form, 10 to 100% by weight of an ethylenicallyunsaturated monomer containing fluorine substituents, have a particlesize of from 10 nm to 100 μm and have been dispersed using an anionicemulsifier and/or an anionic protective colloid in water.
 6. A soliddetergent formulation which comprises: (a) 0.05 to 20% by weight ofcationically modified, particulate, hydrophobic polymers, the surface ofwhich has been cationically modified by coating with cationic polymersand optionally additionally with polyvalent metal ions and/or cationicsurfactants, and the particle size of which is 10 nm to 100 μm, (b) 0.1to 40% by weight of at least one nonionic, cationic and/or anionicsurfactant, (c) 0 to 50% by weight of an inorganic builder, (d) 0 to 10%by weight of an organic cobuilder, and (e) 0 to 60% by weight of othercustomary ingredients, such as extenders, enzymes, perfume, othersurfactants, complexing agents, corrosion inhibitors, bleaches, bleachactivators, bleach catalysts, color transfer inhibitors,antiredeposition agents, soil release polyesters, dyes, dissolutionimprovers and/or disintegrants.
 7. A detergent formulation in liquid orgel form which comprises: (a) 0.05 to 20% by weight of cationicallymodified, particulate, hydrophobic polymers, the surface of which hasbeen cationically modified by coating with at least one cationic polymerand optionally additionally with polyvalent metal ions and/or cationicsurfactants, and the particle size of which is 10 nm to 100 μm, (b) 0.1to 40% by weight of at least one nonionic, cationic and/or anionicsurfactant, (c) 0 to 20% by weight of an inorganic builder, (d) 0 to 10%by weight of an organic cobuilder, (e) 0 to 10% by weight of othercustomary ingredients, such as soda, enzymes, perfume, othersurfactants, complexing agents, corrosion inhibitors, bleaches, bleachactivators, bleach catalysts, color transfer inhibitors,antiredeposition agents, soil release polyesters, dyes, nonaqueoussolvents, hydrotropic agents, thickeners and/or alkanolamines and (f) 0to 90% by weight of water.
 8. A method comprising: treating a textile bycontacting the textile with a mixture comprising one or morecationically modified particulate hydrophobic polymers having acationically modified surface, wherein the cationically modifiedparticulate hydrophobic polymers are obtained by coating one or moreparticulate hydrophobic polymers with one or more cationic polymers,wherein the particle size of the particulate hydrophobic polymers isfrom 10 nm to 100 μm.
 9. The method as claimed in claim 8, wherein thecationically modified particulate hydrophobic polymers are obtained bytreating an aqueous dispersion of the particulate hydrophobic polymerswith an aqueous solution or dispersion of one or more cationic polymers.10. The method of claim 9, wherein the aqueous dispersion comprises ananionic emulsifier, an anionic protective colloid or a mixture thereof.11. The method of claim 8, wherein the particulate hydrophobic polymerscomprise at least one copolymerized anionic monomer.
 12. The method ofclaim 8, wherein a 0.1% strength by weight aqueous dispersion of thecationically modified particulate hydrophobic polymers has an interfacepotential of from −5 to +50 mV.
 13. The method of claim 8, wherein themixture is an aqueous dispersion of the cationically modifiedparticulate hydrophobic polymers having a pH of from 2 to
 12. 14. Themethod of claim 8, wherein the cationically modified particulatehydrophobic polymers are present in an amount of from 0.0002 to 1.0% byweight.
 15. The method of claim 8, wherein the cationically modifiedparticulate hydrophobic polymers are present in an amount of from 0.0002to 0.05% by weight.
 16. The method as claimed in claim 8, wherein thecationic polymers are selected from the groups consisting of polymerscontaining vinylamine units, polymers containing vinylimidazole units,polymers containing quaternary vinylimidazole units, condensates ofimidazole and epichlorohydrin, crosslinked polyamido amines, crosslinkedpolyamidoamines grafted with ethylenimine, polyethylenimines,alkoxylated polyethylenimines, crosslinked polyethylenimines, amidatedpolyethylenimines, alkylated polyethylenimines, polyamines,amine/epichlorohydrin polycondensates, alkoxylated polyamines,polyallylamines, polydimethyldiallylammonium chlorides, polymerscontaining basic (meth)acrylamide esters, polymers containing(meth)acrylic esters, polymers containing basic quaternary(meth)acrylamide units, polymers containing (meth)acrylic ester units,lysinc condensates and mixtures thereof.
 17. The method of claim 8,wherein the cationically modified particulate hydrophobic polymers arefurther modified by coating with one or more polyvalent metal ions,cationic surfactants or mixture thereof.